A novel composite of hierarchically porous carbon (HPC) supported PDMcT-PANI (HPC/PDMcT-PANI) was synthesized through an in situ oxidative polymerization. Field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and Raman spectra showed that a partial amount of PDMcT was parasitized inside of pores of HPC and some other amount of PDMcT formed interpenetrated fibrous electron donor-acceptor PDMcT-PANI adduct with PANI and distributed onto surface of HPC in HPC/PDMcT-PANI composite. X-ray diffraction (XRD) revealed that the interconnected nanoporous structure of HPC and formation of PDMcT-PANI adduct significantly influenced the crystal growth and orientation of PDMcT. As confirmed by the cyclic voltammetry and galvanostatic charge-discharge tests, the incorporation of HPC and PANI had significantly improved the electrochemical performance of PDMcT. It was found that the initial discharge capacity of HPC/PDMcT-PANI composite reached 310 mAh g(-1) and its specific capacity remained 150 mAh g(-1) after 20 cycles. Moreover, the HPC/PDMcT-PANI composite also showed higher specific capacity and better cycling stability than that of its two binary composites [PDMcT-PANI (291 mAh g(-1)) or HPC/PDMcT (253 mAh g(-1))]. (C) 2013 Elsevier Ltd. All rights reserved.